JPH10138372A - Multilayer fuel tube - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin multilayer fuel tube having excellent chemical resistance and permeation preventiveness for gasoline, alcohol gasoline or sour gasoline, excellent flexibility as a tube, and high adhesive strength between resin layers. SOLUTION: The multilayer fuel tube is a multilayer tube obtained by laminating a plurality of layers made of thermoplastic resin. At least one of the layers is formed of polyphenylene sulfide resin composition obtained by blending (B) 10 to 150 pts.wt. of at least one type of functional group-containing thermoplastic resin having at least one type or more bond or functional group selected from amide bond, ester bond, urethane bond, carboxyl group, acid anhydride and epoxy group with (A) 100 pts.wt. of polyphenylene sulfide resin, and the other layers are each formed of (D) thermoplastic resin except polyphenylene sulfide resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin having excellent chemical resistance and permeation resistance to gasoline, alcohol gasoline, sour gasoline, etc., excellent flexibility as a tube, and high adhesion strength between resin layers. The present invention relates to a resin-made multilayer fuel tube.

[0002]

2. Description of the Related Art Polyamide resins are widely used in automobile parts, electric parts, and general equipment parts because of their excellent strength, toughness, fatigue resistance, wear resistance, and moldability. ing.

[0003] Above all, flexible polyamide resins are widely applied as tubes for automobiles, automatic machines, robots, etc., and hose inner tubes, but do not satisfy the required characteristics under severe use conditions.
For example, when it is used for an automobile fuel tube, there is a problem that it is not sufficient for the problem of environmental pollution and permeation prevention of gasoline or alcohol gasoline required for improving fuel efficiency.

[0004] As a method for improving the fuel oil permeability of a polyamide resin tube, a method of blending a polyamide resin with another thermoplastic resin having a low fuel oil permeability, a method of blending a polyamide resin and a fuel oil with a low permeability, or the like. A method of forming a multilayer structure with a small amount of another thermoplastic resin has been conventionally developed.

That is, as a method of blending a polyamide resin with a resin having low fuel oil permeability, for example, a blended resin composition of a soft fluororesin and a nylon resin disclosed in JP-A-3-182538 can be mentioned. ,
This blended resin composition is a molding material having both the chemical resistance of a fluororesin, the mechanical properties of a polyamide resin, and the low-temperature impact resistance. However, an extruded product (tube) using this blend resin has a problem that it is easily torn along the extrusion molding direction, and this tendency is particularly noticeable at low temperatures.

[0006] As a method of forming a multilayer structure of a polyamide resin and another thermoplastic resin having low fuel oil permeability, for example, Japanese Patent Application Laid-Open No. 6-238843 discloses a method in which an inner layer is made of a fluororesin or an adhesive. A soft fluororesin composition in which the layer is made of a soft fluororesin, a polyamide resin and a polyurethane resin, a multilayer molded product in which the outer layer is made of a polyamide resin, and at least one layer other than the polyamide resin shown in JP-A-6-23930, which is made of polyester Examples include multilayer molded articles made of resin, which have high fuel oil permeation prevention properties. However, in the former case, there is a problem that a special extruder for a fluororesin is required, and the low-temperature impact resistance of the molded product is not sufficient.In the latter case, the heat aging resistance of the molded product, There was a problem that the impact resistance was not sufficient.

On the other hand, polyphenylene sulfide resin (hereinafter abbreviated as PPS resin) is an engineering plastic excellent in heat resistance, hot water resistance, chemical resistance, friction and wear resistance, flame retardancy, electric properties, and the like. -Demand for applications such as electronic parts and automobile parts is increasing. Recently, a hollow molding material utilizing the features of the PPS resin has already been described in Japanese Patent Publication No. 6-98673.

However, since the molding temperature of the PPS resin hollow molding material is high and the solidification rate of the resin is high, it is necessary to set the mold temperature to a high temperature in order to obtain a good product appearance. In terms of formability and economy, it was not a very preferable material.

[0009]

Therefore, the properties of the PPS resin such as heat resistance, hot water resistance, chemical resistance and gas permeation resistance, and the moldability of the thermoplastic resins such as polyamide resin and saturated polyester resin, In order to obtain a molded article having characteristics such as economy, it is conceivable to laminate these two materials to form a multilayer hollow molded article.

However, even if the PPS resin layer and another thermoplastic resin layer are simply laminated, there is no adhesion between the two materials, so that peeling occurs between the respective resin layers, and the intended laminated molded product cannot be obtained. I couldn't get it.

For this purpose, a method has been proposed in which an adhesive layer is interposed between a PPS resin layer and a thermoplastic resin layer. For example, a laminated structure in which a PPS resin layer and a polyolefin resin layer are laminated via an adhesive has been proposed. The body is disclosed in JP-A-5-19306.
However, the method of interposing an adhesive layer, for example, increases the number of extruders when obtaining a multilayer structure by co-extrusion molding, so that the processing equipment becomes complicated and processing is troublesome. Therefore, there is a problem that it is economically disadvantageous and industrially undesirable. The present invention has been achieved as a result of studying solving the problems in the above-described conventional technology as a problem.

Accordingly, an object of the present invention is to provide gasoline,
An object of the present invention is to provide a multi-layer fuel tube made of a thermoplastic resin, which is excellent in chemical resistance and permeation resistance to alcohol gasoline, sour gasoline, and the like, has excellent flexibility as a tube, and has high adhesion strength between resin layers.

[0013]

The present inventors evaluated the gasoline permeability and the adhesion between resin layers of a multilayer tube obtained by co-extrusion of a PPS resin and other thermoplastic resins. By using a PPS resin composition containing a specific amount of another thermoplastic resin in a specific amount, it is possible to obtain a tube having both gasoline barrier properties of the PPS resin and excellent mechanical properties of the thermoplastic resin. Heading, the present invention has been reached. That is,
The present invention is as follows.

(1) A multilayer tube formed by laminating a plurality of layers made of a thermoplastic resin, wherein at least one layer is composed of (A) an amide bond and an ester bond per 100 parts by weight of the polyphenylene sulfide resin. Polyphenylene comprising 10 to 150 parts by weight of a functional group-containing thermoplastic resin having at least one bond or functional group selected from urethane bonds, carboxyl groups, acid anhydride groups and epoxy groups. A multilayer fuel tube comprising a sulfide-based resin composition, wherein the other resin layer comprises a thermoplastic resin other than (D) polyphenylene sulfide resin.

(2) The thermoplastic resin other than (D) polyphenylene sulfide resin has a Young's modulus of 15,000 kg / c.
The polyphenylene sulfide resin composition for multilayer hollow molding according to the above (1), which is a thermoplastic resin having a m ² or less.

(3) The polyphenylene sulfide resin composition for multilayer hollow molding according to the above (1) or (2), wherein the (A) polyphenylene sulfide resin is deionized.

(4) The polyphenylene sulfide resin composition for multilayer hollow molding according to the above (1) to (3), wherein the epoxy group is a glycidyl group.

(5) The functional group-containing thermoplastic resin (B) is
(1) to (4), which are at least one selected from a polyamide resin, a polyester resin, a polyurethane resin, and a modified polyolefin resin.
A multi-layer fuel tube as described.

(6) When the modified polyolefin resin is (B)
') The multi-layer fuel tube according to the above (5), which is an epoxy group-containing modified olefin-based copolymer containing α-olefin and glycidyl ester of α, β-unsaturated acid as main components.

(7) The functional group-containing thermoplastic resin (B)
(1) to (1) to (1) to (1), wherein the mixture is a mixture of at least one selected from a polyamide resin, a polyester resin, and a polyurethane resin and a modified polyolefin resin in a weight ratio of 1/2 to 2/1. The multilayer fuel tube according to (6).

(8) The polyphenylene sulfide-based resin composition further comprises (C) 50 parts by weight or less of an elastomer containing no glycidyl group, carboxyl group or acid anhydride group, based on 100 parts by weight of the polyphenylene sulfide resin. The multilayer fuel tube according to any one of the above (1) to (7), wherein:

(9) (D) The thermoplastic resin according to the above (1) to (8), wherein the thermoplastic resin is at least one selected from a polyamide resin, a polyester resin, a polyurethane resin, and a polyolefin resin. Multilayer fuel tube.

(10) The multilayer fuel tube according to the above (1) to (9), which is used as a tube for an internal combustion engine.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the components and the structure of a multilayer tube for an internal combustion engine according to the present invention will be specifically described.

The (A) PPS resin used in the present invention is a polymer containing at least 70 mol%, preferably at least 90 mol% of a repeating unit represented by the following structural formula. It is not preferable because heat resistance is impaired.

[0026]

Embedded image Generally, as the PPS resin, a polymer having a relatively small molecular weight obtained by the production method represented by JP-B No. 45-3368 and an essential polymer obtained by the production method represented by JP-B No. 52-12240 are disclosed. And linear and relatively high molecular weight polymers.
The polymer obtained by the method described in JP-A No. 8 can be used after polymerization by heating in an oxygen atmosphere, or by adding a crosslinking agent such as a peroxide and heating to increase the degree of polymerization. It is.

In the present invention, a PPS resin obtained by any method can be used, but an essentially linear polymer having a relatively high molecular weight is preferably used.

In the (A) PPS resin, less than 30 mol% of the repeating unit can be constituted by a repeating unit having the following structural formula.

[0029]

Embedded image The (A) PPS resin used in the present invention may be one that has been subjected to the above-mentioned polymerization step, and has been subjected to a deionization treatment by an acid aqueous solution washing treatment, a hot water washing treatment, an organic solvent washing treatment, or the like. desirable.

The above-mentioned acid aqueous solution washing treatment is performed as follows. That is, the acid used in the cleaning treatment of the PPS resin with the acid aqueous solution in the present invention is not particularly limited as long as it does not have an action of decomposing the PPS resin.
Examples thereof include hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid, carbonic acid and propyl acid. Among them, acetic acid and hydrochloric acid can be more preferably used, but those which decompose and degrade PPS resin such as nitric acid are not preferred.

As a method of washing with an aqueous acid solution, there is a method of immersing a PPS resin in an aqueous solution of an acid or the like, and if necessary, stirring or heating can be appropriately performed. For example, when acetic acid is used, an aqueous solution having a pH of 4 is heated to 80 to 90 ° C.
A sufficient effect can be obtained by immersing the PPS resin powder while stirring the mixture for 30 minutes. It is necessary to wash the PPS resin subjected to the acid treatment several times with water or warm water in order to physically remove the remaining acid or salt.

The water used for the washing is preferably distilled water or deionized water in the sense that the effect of the preferred chemical modification of the PPS resin by the acid treatment is not impaired.

The case where the hot water cleaning treatment is performed is as follows. That is, the PPS used in the present invention
When treating the resin with hot water, the temperature of hot water should be 100
It is important that the temperature is not less than 100 ° C, more preferably not less than 120 ° C, still more preferably not less than 150 ° C, particularly preferably not less than 170 ° C.

The water used for exhibiting the preferable chemical modification effect of the PPS resin by the hot water washing treatment of the present invention is preferably distilled water or deionized water.
The operation of the hot water treatment is usually performed by charging a predetermined amount of PPS resin, heating and stirring in a pressure vessel. The proportion of the PPS resin and water is preferably as high as possible, but a bath ratio of 200 g or less of PPS resin to 1 liter of water is usually selected.

In the atmosphere of the hot water treatment, decomposition of the terminal groups is not preferable, and therefore, it is preferable to use an inert atmosphere to avoid this. Further, it is preferable to wash the PPS resin after the hot water treatment operation several times with warm water in order to physically remove the remaining components.

Further, the case of the organic solvent washing treatment is as follows. That is, the organic solvent used for washing the PPS resin in the present invention is not particularly limited as long as it does not have an action of decomposing the PPS resin. For example, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, 1,3 -Dimethylimidazolidinone, hexamethylphosphoramide, nitrogen-containing polar solvents such as piverazinones, dimethyl sulfoxide, dimethyl sulfone,
Sulfoxides such as sulfolane, sulfone solvents, ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, acetophenone, ether solvents such as dimethyl ether, dipropyl ether, dioxane, tetrahydrofuran, chloroform, methylene chloride, trichloroethylene, ethylene chloride, park Roll ethylene,
Halogen solvents such as monochloroethane, dichloroethane, tetrachloroethane, perchloreethane, and chlorobenzene; alcohols such as methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, phenol, cresol, polyethylene glycol, and polypropylene glycol . Examples include phenol solvents and aromatic hydrocarbon solvents such as benzene, toluene, and xylene.
Among these organic solvents, the use of N-methylpyrrolidone acetone, dimethylformamide, chloroform and the like is particularly preferred. In addition, these organic solvents include 1
It is used in a kind or a mixed system of two or more kinds.

As a washing method using an organic solvent, there is a method of immersing a PPS resin in an organic solvent, and the like, and if necessary, stirring or heating can also be performed.

The washing temperature when washing the PPS resin with an organic solvent is not particularly limited, and an arbitrary temperature from ordinary temperature to about 300 ° C. can be selected. Here, the higher the cleaning temperature, the higher the cleaning efficiency tends to be.
A sufficient effect can be obtained at a washing temperature of 50 ° C.

It is also possible to wash under pressure at a temperature not lower than the boiling point of the organic solvent in a pressure vessel. The washing time is not particularly limited and depends on the washing conditions, but in the case of batch washing, a sufficient effect is usually obtained by washing for 5 minutes or more. In addition, it is also possible to wash continuously.

A sufficient effect can be obtained only by washing the PPS resin formed by polymerization with an organic solvent, but it is preferable to combine the washing with water or washing with warm water in order to further exert the washing effect. When a high-boiling water-soluble organic solvent such as N-methylpyrrolidone is used, washing with water or warm water after washing with the organic solvent is preferable because the remaining organic solvent can be easily removed.

The melt viscosity of the (A) PPS resin used in the present invention is not particularly limited, and any melt viscosity can be used as long as it can be kneaded with the (B) functional group-containing thermoplastic resin and the (C) other thermoplastic resin. Although those having a melt viscosity can be used, those having a melt viscosity of 100 to 10,000 poise at 320 ° C. and a shear rate of 10 sec ^-1 are usually used.

The thermoplastic resin (B) having a functional group used in the present invention includes one or more bonds or functional groups selected from an amide bond, an ester bond, a urethane bond, an acid anhydride group and an epoxy group. Specifically, it is at least one selected from a polyamide resin, a saturated polyester resin, a polyurethane resin, and a modified polyolefin resin.

Here, the polyamide resin is an amino acid,
It is a polyamide containing lactam or diamine and dicarboxylic acid as main components. Representative examples of the main components include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and paraaminomethylbenzoic acid, ε-aminocaprolactam,
lactams such as ω-laurolactam, tetramethylenediamine, hexamerenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,
4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, metaxylenediamine, paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3 , 5,5-Trimethylcyclohexane, bis (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, aminoethylpiperazine Aliphatic, alicyclic, aromatic diamines, and adipic acid, speric acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, etc.
Aliphatic, alicyclic and aromatic dicarboxylic acids such as isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid and hexahydroisophthalic acid In the present invention, a polyamide homopolymer or copolymer derived from these raw materials can be used alone or in the form of a mixture.

In the present invention, particularly useful polyamide resins include polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66), polytetramethylene adipamide (nylon 46), and polyhexamethylene sebaca. Amide (nylon 610), polyhexamethylene dodecamide (nylon 612), polydodecaneamide (nylon 12), polyundecaneamide (nylon 11), polyhexamethylene terephthalamide (nylon 6T), polyxylylene adipamide (nylon XD
6) and mixtures or copolymers thereof.

The degree of polymerization of these polyamide resins is not particularly limited, and the relative viscosity measured at 25 ° C. in a 1% concentrated sulfuric acid solution is in the range of 1.5 to 7.0, especially 2.0 to 6. 5
Are preferred.

The polyester resin used herein is preferably a resin having an aromatic relation derived from terephthalic acid. An aromatic polyester obtained from a dicarboxylic acid whose terephthalic acid is at least 60 mol% and an aliphatic diol is preferred. Particularly preferred. Examples of dicarboxylic acids other than terephthalic acid include azelaic acid, sebacic acid, adipic acid, aliphatic dicarboxylic acids having 2 to 20 carbon atoms such as dodecanedicarboxylic acid, isophthalic acid, aromatic dicarboxylic acids such as naphthalenedicarboxylic acid, and cyclohexanedicarboxylic acid. An alicyclic dicarboxylic acid such as an acid may be used alone or as a mixture. Aliphatic diols include ethylene glycol, propylene glycol, 1,4-butanediol, trimethylene glycol, hexamethylene glycol, and the like.

Preferred examples of the polyester used in the present invention include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, and polycyclohexylene dimethylene terephthalate. 60 mol% or more, preferably 7 mol% of polybutylene terephthalate or terephthalic acid.
A copolymer polyester comprising a dicarboxylic acid component containing 0 mol% or more of dodecanedicarboxylic acid and / or isophthalic acid and a 1,4-butanediol component is particularly preferably used.

The degree of polymerization of these polyester resins, particularly preferably used polybutylene terephthalate (hereinafter abbreviated as PBT resin) and copolymerized polyester, is not particularly limited, and a 0.5% orthochlorophenol solution was measured at 25 ° C. Those having a relative viscosity in the range of 0.5 to 2.5, particularly 0.8 to 2.0 are preferred. Also, the degree of polymerization of polyethylene terephthalate is not particularly limited, and the intrinsic viscosity of the 0.5% orthochlorophenol solution measured at 25 ° C. is in the range of 0.54 to 1.5, especially 0.1.
Those having a range of 6 to 1.2 are preferred.

The polyurethane resin used here is a chain polymer comprising a polyisocyanate and a diol, and specific examples of the polyisocyanate include 2,4.
-Tolylene diisocyanate, hexamethylene diisocyanate, meta-xylene diisocyanate, and 4,
4'-diphenylmethane diisocyanate and the like. Diols include polyester type and polyether type. Specific examples of the former include phthalic acid, adipic acid,
Those composed of organic acids such as dimerized linoleic acid and maleic acid and glycols such as ethylene, propylene, butylene and diethylene are specific examples of the latter, such as polyoxypropylene glycol, poly (oxypropylene) poly (oxy Methylene) glycol, poly (oxybutylene) glycol, poly (oxytetramethylene) glycol, and the like are each generally used.

The degree of polymerization of these polypolyurethanes is not particularly limited, but is usually 220 ° C. and a shear rate of 10 / sec.
Having a melt viscosity of 1,000 to 100,000 poise is used.

Further, the modified polyolefin resin used here is an olefin polymer having a functional group selected from an epoxy group, a carboxyl group, an acid anhydride group and the like in a side chain or a main chain.

As the epoxy group-containing polyolefin polymer, an olefin copolymer having a glycidyl ester or glycidyl ether in a side chain or an olefin copolymer having a double bond can be epoxidized. And the like.

As the polyolefin polymer containing a carboxyl group and an acid anhydride group, an organic acid and a peroxide such as maleic acid, succinic acid, phthalic acid, or an acid anhydride thereof are added to a polyolefin resin, and the mixture is heated and melted. And the like.

In the present invention, among these modified polyolefin resins, (B ′) α-olefin and α, β
-A modified polyolefin copolymer comprising a glycidyl ester of an unsaturated carboxylic acid is preferably used.

Here, specific examples of the α-olefin which is one of the monomer components of the modified olefin resin include ethylene, propylene, butene-1, 4-methylpentene-1, hexene1, decene-1, and Octene-1 and the like, among which ethylene is preferably used. Further, two or more of them can be used simultaneously.

On the other hand, (B ') which is a representative example of the modified olefin resin, the monomer component α, β- is a monomer component in the modified polyolefin copolymer composed of α-olefin and glycidyl ester of α, β-unsaturated carboxylic acid. The unsaturated acid glycidyl ester is a compound represented by the following general formula, and specifically includes glycidyl acrylate, glycidyl methacrylate, and glycidyl ethacrylate, among which glycidyl methacrylate is particularly preferably used. .

[0057]

Embedded image (However, R in the formula represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.) Such a modified polyolefin-based copolymer is a random mixture of the α-olefin and the glycidyl ester of an α, β-unsaturated acid. , Block or graft copolymers.

The copolymerization amount of the glycidyl ester of the α, β-unsaturated acid in the olefin copolymer mainly containing the glycidyl ester of the α-olefin and the α, β-unsaturated acid is 1 to 50% by weight. , Preferably in the range of 3 to 40% by weight. If the copolymerization amount is less than 1% by weight, the intended effect is insufficient, and if it exceeds 50% by weight, a gel is formed at the time of melt-kneading with the PPS resin, which adversely affects extrusion stability, moldability, mechanical strength, and the like. May have an effect.

In the present invention, the mixing ratio of each resin in the PPS resin composition forming one resin layer is as follows:
At least one kind selected from the functional group-containing thermoplastic resin (B) is used in an amount of 10 to 1 based on 100 parts by weight of the PPS resin.
It is in the range of 50 parts by weight, preferably 40 to 130 parts by weight, more preferably 60 to 120 parts by weight, and if it is less than 10 parts by weight, the adhesion between the layer made of the PPS resin composition and the other layer is small, and Exceeding the part is not preferable because the gasoline barrier property of the multilayer molded article is reduced.

In the above PPS resin composition,
The adhesion strength between the layer made of the PPS resin composition and another thermoplastic resin layer is increased by blending one or more kinds of the thermoplastic resin (B) with the (A) PPS resin. However, in order to further increase the adhesiveness between the layer made of the PPS resin composition and other layers, it is possible to (A) mix the (B) functional group-containing heat with the PPS resin. Modified polyolefin resin containing a plastic resin selected from a polyamide resin, a saturated polyester resin and a polyurethane resin, and further containing (B ′) at least one or more selected from a glycidyl group, a carboxyl group, and an acid anhydride group. In particular, it is desirable to use a modified polyolefin-based copolymer comprising an α-olefin and a glycidyl ester of an α, β-unsaturated carboxylic acid in combination.

In this case, the blend ratio of at least one selected from the group consisting of a polyamide resin, a polyester resin and a polyurethane resin to the (B ′) modified polyolefin resin is in the range of 1/2 to 2/1 (weight ratio). It is preferable that the blend ratio be within this range, so that a more practical interlayer adhesion strength can be obtained.

In the present invention, if necessary, (C) an elastomer containing no glycidyl group, carboxyl group or acid anhydride group may be added to the PPS resin composition. Can obtain an advantageous effect that the extrusion moldability of the PPS resin is improved.

Examples of the (C) elastomer containing no glycidyl group, carboxyl group, or acid anhydride group include polyolefin elastomers, diene elastomers, and acrylic elastomers.

Specific examples of the polyolefin-based elastomer include an ethylene-propylene copolymer, an ethylene-butene copolymer, a polybutene, an ethylene-propylene-diene copolymer, and an ethylene-vinyl acetate copolymer.

Specific examples of the diene elastomer include styrene-butadiene copolymer, polybutadiene, butadiene-acrylonitrile copolymer, polyisoprene, butene-isoprene copolymer, and styrene-ethylene-butadiene-styrene copolymer. These hydrogenated products such as coalescence can be mentioned.

Specific examples of the acrylic elastomer include ethylene-methyl acrylate copolymer and ethylene-methyl acrylate.
Ethyl acrylate copolymer, ethylene-acrylic acid n-
Propyl copolymer, ethylene-isopropyl acrylate copolymer, ethylene-n-butyl acrylate copolymer,
Ethylene-t-butyl acrylate copolymer, ethylene-
Isobutyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl methacrylate copolymer, ethylene-n-propyl methacrylate copolymer,
Olefin- (meth) acrylate such as ethylene-isopropyl methacrylate copolymer, ethylene-n-butyl methacrylate copolymer, ethylene-t-butyl methacrylate copolymer, ethylene-isobutyl methacrylate copolymer Polymer, acrylate copolymer,
Methyl acrylate-acrylonitrile copolymer, methyl methacrylate-acrylonitrile copolymer, propyl acrylate-acrylonitrile copolymer, propyl methacrylate-acrylonitrile copolymer, butyl acrylate-acrylonitrile copolymer, methacrylic acid (Meth) acrylic acid ester-acrylonitrile copolymer such as butyl-acrylonitrile copolymer and the above-mentioned butadiene-acrylonitrile copolymer.

When the elastomer (C) is used, the amount thereof is preferably 50 parts by weight or less, particularly preferably 10 to 50 parts by weight, based on 100 parts by weight of the (A) PPS resin composition.

In the present invention, as the thermoplastic resin other than the (D) PPS resin used for lamination with the PPS resin composition, at least one kind selected from a polyamide resin, a polyester resin, a polyurethane resin and a polyolefin resin is used. These have a Young's modulus of 15,000
kg / cm ² or less, is preferably used particularly 12000kg / cm ² or less. At this time, the resin may include a plasticizer, and the Young's modulus in that case is a measured value of the resin (composition) including the plasticizer.

(D) The thermoplastic resin has a Young's modulus of 1500
If it exceeds 0 kg / cm ² , the flexibility of the tube is insufficient, and the kink tends to be generated during bending, which is not preferable.

The measurement of the Young's modulus is performed according to ASTM D638.

Here, among the thermoplastic resins (D), the polyamide resin, the polyester resin and the polyurethane resin are the same as the thermoplastic resins described in the above (B), and therefore the description is omitted.

The polyolefin resin used here includes polyethylene, polypropylene, chlorinated polyethylene, chlorinated polypropylene, and polymethylpentene.

The (B) functional group-containing thermoplastic resin contained in the layer made of the PPS resin composition and the (D) thermoplastic resin forming another layer are exemplified by polyamide resin. For example, if the (B) functional group-containing thermoplastic resin in the PPS resin composition layer is a polyamide resin, the combination (D) of the thermoplastic resin in the multilayer is also the same type of polyamide resin, and the combination between the respective resin layers This is a preferable condition for developing excellent adhesion strength.
Further, among polyamide resins, for example, if the thermoplastic resin (B) having a functional group in the PPS resin composition layer is nylon 6, the thermoplastic resin (D) is also nylon 6, in view of adhesion. More preferably, even if the thermoplastic resin (D) is another polyamide resin such as nylon 66 or nylon 11, good adhesion can be obtained.

In the present invention, the PPS resin composition comprises at least one of a polyamide resin, a saturated polyester resin, and a polyurethane resin (B) among functional group-containing thermoplastic resins, and (B ′) a modified polyolefin. It is as described above that a stronger adhesion strength can be obtained between (D) and the thermoplastic resin layer by blending together with the base resin.

Further, a PPS resin composition comprising (A) a PPS resin used in the present invention, (B) a thermoplastic resin having a functional group, and (C) an elastomer compounded as required, and laminating the same. (D) In the thermoplastic resin layer, a polyalkylene oxide oligomer-based compound, a thioether-based compound, or the like, as long as the effects of the present invention are not impaired.
Ester compounds, plasticizers such as organic phosphorus compounds, talc, kaolin, crystal nucleating agents such as organic phosphorus compounds, mold release agents, antioxidants, heat stabilizers, lubricants, and purple Flammability and conductivity can be imparted, and other layers having these properties can be added.

The method of preparing the PPS resin composition of the present invention, that is, the method of mixing (A) a PPS resin with a (B) functional group-containing thermoplastic resin and, if necessary, (C) an elastomer, is particularly preferred. It is not limited.

For example, after preliminarily mixing with an appropriate mixer, supplying to an extruder, melt-kneading and pelletizing,
A method of directly supplying the mixture to a molding machine and a method of directly supplying a mixture obtained by dry blending with a mixer to a molding machine may be exemplified, but the method is not necessarily limited thereto.

The method for producing the multilayer fuel tube of the present invention is not particularly limited, and the molten resin extruded from the extruder having the number of layers or the number of materials is introduced into one multilayer tube die. By bonding them in a die or immediately after the die is taken out, a multilayer tube can be manufactured. Alternatively, a method may be used in which a single-layer tube is once manufactured, and another layer is laminated inside or outside the tube to manufacture a multilayer tube.

When a multilayer tube having a multilayer structure of three or more layers is manufactured, extruders are appropriately added, each extruder is connected to a co-extrusion die, and a multilayer parison is extruded. Is obtained by

PPS in Multilayer Fuel Tube of the Present Invention
The layer composition of the resin composition and the thermoplastic resin (D) is such that the layer composed of the PPS resin composition is an inner layer and the (D) thermoplastic resin layer is an outer layer in order to maximize the chemical resistance of the PPS resin. The configuration is most preferable, but is not necessarily limited to this. For example, the reverse of the above may be adopted. Further, in the case of three layers, any resin may be selected as the intermediate layer. it can. The number of layers is two or more, and may be four or more.

The multilayer fuel tube of the present invention thus formed is excellent in chemical resistance and gas permeation resistance to gasoline, alcohol gasoline, sour gasoline and the like, is excellent in flexibility as a tube, and has high adhesion strength between resin layers. It is preferably applied to internal combustion engines such as automobiles.

[0082]

The present invention will be described more specifically with reference to the following Examples and Comparative Examples, but the present invention is not limited to these Examples.

The evaluation of adhesion strength and alcohol gasoline permeability in the following Examples and Comparative Examples was performed by the following methods.

[Adhesion Strength] A tube was cut into a strip shape, the inner layer and the outer layer at the end of the strip were peeled off, each layer was sandwiched between chucks of a tensile tester, and a 180 ° peel strength (gf / 10 mm) was obtained under the following conditions. ) Was measured.

B. Adhesion strength: 10 mm / min b. Test piece size: width 5 mm, length: 100 mm [Gasoline permeability] A tube cut into a length of 30 cm is sealed with one end, and an alcohol gasoline mixture obtained by mixing commercially available regular gasoline and methyl alcohol at a ratio of 85 to 15 is put therein. The other end was also sealed. Thereafter, the total weight was measured, and the test tube was placed in a 40 ° C. oven, and the alcohol gasoline permeability was evaluated based on the change in weight.

Reference Example 1 (Polymerization of PPS resin) In an autoclave, 3.20 kg (25 mol, containing 40% of crystallization water) of sodium sulfide, 4 g of sodium hydroxide, 1.36 kg of sodium acetate trihydrate (about 10 mol) ) And N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) 7.9k
g of water and gradually heated to 205 ° C. while stirring to remove about 1.5 liters of extracted water containing 1.36 kg of water.

3.75 kg (25.5 mol) of 1,4-dichlorobenzene and 2 kg of NMP were added to the residual mixture, and the mixture was heated at 265 ° C. for 3 hours.

The reaction product was washed 5 times with 70 ° C. hot water,
By drying under reduced pressure at 80 ° C. for 24 hours, powder PP
About 2 kg of S resin was obtained.

Comparative Example 1 The PPS resin obtained in Reference Example 1 was supplied to a hopper of a 40 mmφ single screw extruder, melt-kneaded at a cylinder temperature of 300 ° C. and a rotation speed of 80 rpm, and pelletized.

In the inner layer of the tube, the pelletized P
Nylon 11 (toray Co., Ltd. "Rilsan" BESN BK P20) having a PS resin and a plasticizer added to the outer layer at about 7% by weight.
TL) (Young's modulus 5000 kg / cm ² )
A layer tube was formed.

The molding apparatus has two extruders,
A die formed by collecting the resin discharged from the two extruders by an adapter and forming the same into a tube, a sizing die for cooling the tube and controlling the size, and a take-off machine were used.

The obtained two-layer tube had an outer diameter of 8 mm,
Inner diameter: 6 mm, outer layer thickness: 0.9 mm, inner layer thickness:
0.1 mm.

The evaluation results of this two-layer tube are as shown in Table 1. When a PPS resin is used as the barrier layer for alcohol gasoline, an improvement in the anti-permeability is observed. And the adhesion strength between them was very poor.

[Examples 1 to 5 and Comparative Example 2] The thermoplastic resin having a functional group was replaced with nylon 11 (“Rilsan” BES, manufactured by Toray Industries, Inc.) in comparison with the PPS resin obtained in Reference Example 1.
NBK P20TL), nylon 12 (Toray Industries, Inc.)
"Rilsan" AESN BK P20TL), nylon 6 (Toray Industries, Inc. "Amilan" CM1046X04), modified polyolefin resin (ethylene / glycidyl methacrylate (88/12) copolymer), and Mitsui Petrochemical Co., Ltd. as an elastomer "Toughmer" A4085
Was used in the inner layer side, and as shown in Table 1, nylon 11 or nylon 12 was used in the outer layer side, and the same as in Comparative Example 1 above. A two-layer tube was formed under the conditions described in the above.

Table 1 shows the evaluation results of the obtained two-layer tubes.
As shown in the above, when a polyamide resin is blended with the PPS resin, the adhesion strength between the layers tends to be improved,
When a modified polyolefin resin (ethylene / glycidyl methacrylate copolymer) and an elastomer are used in combination with the polyamide resin, PPS is obtained.
It is apparent that the adhesion strength between the resin composition layer and the polyamide resin layer is further enhanced, and that excellent barrier properties of alcohol gasoline are exhibited.

However, for 100 parts by weight of the PPS resin,
When the functional group-containing thermoplastic resin and the elastomer are blended in a total amount of 150 parts by weight or more (Comparative Example 2), it is apparent that the barrier property of alcohol gasoline is undesirably reduced.

[0097]

[Table 1] [Examples 6 to 8] In Example 1, the outer layer was made of a thermoplastic resin made of a polyester resin (Toray Industries, Inc., 5201-X1).
1, Young's modulus 15000 kg / cm ² ), polyurethane resin (Takeda Birdish Urethane Industry Co., Ltd., “Elastollan” 1164D, Young's modulus 3000 kg / c)
m ² ) or a polyolefin resin (Mitsui Petrochemical Co., Ltd., “HIZEX” 3000B, Young's modulus 100
00 kg / cm ² ) and the inner layer was changed to Reference Example 1.
As the functional group-containing thermoplastic resin, a polyurethane resin (Showa Denko KK, "Elastolane" E598PNAT) and a modified polyolefin resin (ethylene / glycidyl methacrylate (88/12))
Copolymer) and an elastomer ("Tuffmer" A4085 manufactured by Mitsui Petrochemical Co., Ltd.) in a ratio shown in Table 2 using a PPS resin composition under the same conditions.
A layer tube was formed.

The evaluation results of the obtained two-layer tube are as shown in Table 2. Even when the resin types of the PPS resin composition layer and other resin layers were changed, good barrier properties against alcohol gasoline and high performance were obtained. Adhesive strength was obtained.

[Comparative Examples 3 and 4] Nylon 11 containing a plasticizer
(Toray Co., Ltd. "Rilsan" BESN BK P20T
L) and nylon 12 containing a plasticizer (“Rilsan” AESN BKP20TL, manufactured by Toray Industries, Inc.), and extruded from one extruder to form a single-layer tube in the same procedure as in Example 1.

As a result of similarly evaluating the barrier properties of alcohol gasoline for each of the obtained single-layer tubes, as shown in Table 2, good barrier properties of alcohol gasoline could not be obtained.

[0101]

[Table 2]

[0102]

As described above, the multi-layer fuel tube of the present invention has excellent chemical resistance and permeation resistance to gasoline, alcohol gasoline, sour gasoline, etc., and also has excellent flexibility as a tube, and also has various resin properties. It has high functional performance with high adhesion strength between layers, and is particularly preferably applied to internal combustion engines such as automobiles.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 23/08 C08L 67/00 67/00 75/04 75/04 77/00 77/00 81/00 81/00 B60K 15 / 02 C

Claims (10)

[Claims] 1. A multilayer tube formed by laminating a plurality of layers made of a thermoplastic resin, wherein at least one layer comprises:
(A) an amide bond, an ester bond, a urethane bond, based on 100 parts by weight of the polyphenylene sulfide resin;
Polyphenylene sulfide resin composition comprising 10 to 150 parts by weight of at least one functional group-containing thermoplastic resin having at least one bond or functional group selected from a carboxyl group, an acid anhydride group and an epoxy group A multi-layer fuel tube, wherein the other resin layer is made of a thermoplastic resin other than (D) polyphenylene sulfide resin. 2. A thermoplastic resin other than (D) a polyphenylene sulfide resin having a Young's modulus of 15,000 kg / cm.
^2. A thermoplastic resin of ² or less.
The polyphenylene sulfide resin composition for multi-layer hollow molding according to the above. 3. The polyphenylene sulfide resin composition for multilayer hollow molding according to claim 1, wherein (A) the polyphenylene sulfide resin has been deionized. 4. The polyphenylene sulfide resin composition for multilayer hollow molding according to claim 1, wherein the epoxy group is a glycidyl group. 5. The thermoplastic resin having a functional group (B) is a polyamide resin, a polyester resin, a polyurethane resin,
The multi-layer fuel tube according to any one of claims 1 to 4, wherein the multi-layer fuel tube is at least one selected from the group consisting of a modified polyolefin resin and a modified polyolefin resin. 6. The modified polyolefin-based resin, wherein (B)
6. The multi-layer fuel tube according to claim 5, which is an epoxy group-containing modified olefin copolymer containing α-olefin and a glycidyl ester of α, β-unsaturated acid as main components. 7. A weight ratio of (B) at least one kind of thermoplastic resin containing functional group selected from polyamide resin, polyester resin and polyurethane resin and a modified polyolefin resin in a weight ratio of 1/2 to 2/1. The multi-layer fuel tube according to claim 1, wherein the multi-layer fuel tube is a mixture obtained by mixing at the same time. 8. The polyphenylene sulfide-based resin composition further comprises (C) 50 parts by weight or less of an elastomer containing no glycidyl group, carboxyl group, or acid anhydride group, based on 100 parts by weight of the polyphenylene sulfide resin. The multilayer fuel tube according to any one of claims 1 to 7, wherein: 9. The method according to claim 1, wherein (D) the thermoplastic resin is at least one selected from a polyamide resin, a polyester resin, a polyurethane resin, and a polyolefin resin. Multi-layer fuel tube. 10. The multi-layer fuel tube according to claim 1, which is used as a tube for an internal combustion engine.